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. 2022 Oct 22;27(21):7156.
doi: 10.3390/molecules27217156.

Push-Pull Structures Based on 2-Aryl/thienyl Substituted Quinazolin-4(3 H)-ones and 4-Cyanoquinazolines

Tatyana N Moshkina  1 , Emiliya V Nosova  1   2 , Julia V Permyakova  1 , Galina N Lipunova  2 , Ekaterina F Zhilina  2 , Grigory A Kim  1   2 , Pavel A Slepukhin  1   2 , Valery N Charushin  1   2
Affiliations

Push-Pull Structures Based on 2-Aryl/thienyl Substituted Quinazolin-4(3 H)-ones and 4-Cyanoquinazolines

Tatyana N Moshkina et al. Molecules. .

Abstract

Design and synthesis of 2-(aryl/thiophen-2-yl)quinazolin-4(3H)-ones and 4-cyano-2-arylquinazolines with Et2N-, Ph2N- or carbazol-9-yl- electron donating fragment are described. The key photophysical properties of these compounds have been studied by UV/Vis absorption and fluorescence spectroscopy in solvents of different polarity (toluene and MeCN). 2-(Aryl/thiophen-2-yl)quinazolin-4(3H)-ones show fluorescence in blue-green region in toluene solution with quantum yields up to 89% in the case of 2-(4'-N,N-diphenylamino[1,1'-biphenyl]-4-yl)-quinazolin-4(3H)-one. Moreover, triphenylamino derivative based on quinazolin-4(3H)-one with para-phenylene linker displays the highest quantum yield of 40% in powder. The fluorescence QY of Et2N and Ph2N derivatives decrease when going from toluene to MeCN solution, whereas carbazol-9-yl counterparts demonstrate strengthening of intensity that emphasizes the strong influence of donor fragment nature on photophysical properties. 4-Cyanoquinazolines are less emissive in both solvents, as well as, in solid state. The introduction of cyano group into position 4 leads to orange/red colored powder and dual emission bands. Some molecules demonstrate the increase in emission intensity upon addition of water to MeCN solution. According to frontier molecular orbitals (HOMO, LUMO) calculations, the energy gap of 4-cyanoquinazoline decreases by more than 1 eV compared to quinazolin-4-one, that is consistent with experimental data.

Keywords: 2-(biphenyl)quinazoline; 2-thienylquinazoline; 4-cyanoquinazoline; donor–acceptor systems; fluorescence; quinazolin-4(3H)-one; π-linker.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Representatives of quinazolin-4(3H)-one-containing chromophores.
Scheme 1
Scheme 1
Synthesis of 2-aryl/thienylquinazolin-4(3H)-ones 4–6.
Figure 2
Figure 2
Structure of 2-aryl/thienyl-4-cyanoquinazolines 7–9.
Scheme 2
Scheme 2
Synthesis of 2-(4-diphenylamino)phenyl-4-cyanoquinazoline (11).
Figure 3
Figure 3
(a) Molecular structure of 11 in the thermal ellipsoids of 50% probability; (b) Selected torsion angles of compound 11.
Figure 4
Figure 4
(a) UV/Vis (dashed line) and photoluminescence (solid line) spectra of compounds 5a–c in toluene; (b) UV/Vis (dashed line) and photoluminescence (solid line) spectra of Ph2N derivatives 4b, 5b, 6b and 10 in toluene.
Figure 5
Figure 5
UV/Vis (dashed line) and photoluminescence (solid line) spectra of 4-cyano-derivatives 8a,b, 9 and 11 in toluene (a) and MeCN (b).
Figure 6
Figure 6
Emission of compounds 4–11 in solid state (powder). Photographs were taken in the dark upon irradiation with a hand-held UV lamp (λem = 366 nm).
Figure 7
Figure 7
(a) Normalized emission spectra of quinazolinones 4–6, 10 in solid state; (b) The CIE chromaticity diagram of blue chromophores 5a–c, 6b,c in solid state.
Figure 8
Figure 8
Diagram on HOMO and LUMO energy levels of quinazolin-4(3H)-ones 4a–c, 5a–c, 6a–c, 10 and 4-cyanoquinazolines 8a,b, 9, 11 in gas phase.
See this image and copyright information in PMC

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